Abiogenic Aragonite Research Articles

Isotopic and mineralogic bias introduced by pulverization of aragonite

RationaleStable carbon and oxygen isotope data of biogenic and abiogenic aragonite are of fundamental relevance in paleoclimate research. Wet‐chemical analysis of such materials requires well‐homogenized, fine‐grained powder. In the present study, the effect of different grinding/milling methods on sample homogeneity and the potential risk of unintentional calcite formation and isotope shift were evaluated.MethodsShells of Arctica islandica and aragonite sputnik crystals were pulverized using a set of commonly used methods, including a hand‐held drill, a vibromill operated at various settings (with and without liquid nitrogen cooling, changes in ball diameters, frequencies, and processing durations), and an agate mortar and pestle. Stable isotope values were measured using an isotope ratio mass spectrometer operated in continuous flow mode. Identification of mineral phases was obtained by powder X‐ray diffraction (PXRD), Raman spectroscopy, and attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy. Calcite content was quantified by PXRD Rietveld refinement.ResultsSamples showed substantial homogeneity, in particular after vibromilling (duration 3–10 min). More vigorous grinding resulted in larger fractions of calcite (0.5–4.2 wt%) and a concomitant δ18O and δ13C decrease, specifically in bivalve shells. The only method for producing pure aragonite powder was by pounding the aragonite sputniks manually with an agate mortar and pestle.ConclusionsNone of the studied, commonly used machine‐based pulverization methods produced pure aragonite powder from samples consisting originally of aragonite. These findings have significant implications for light‐stable isotope‐based paleoclimate reconstructions. Except for abiogenic aragonite powder produced by pounding in an agate mortar, paleotemperatures would be overestimated.

Temperature Dependence of Clumped Isotopes (∆47) in Aragonite.

Clumped isotope thermometry can independently constrain the formation temperatures of carbonates, but a lack of precisely temperature-controlled calibration samples limits its application on aragonites. To address this issue, we present clumped isotope compositions of aragonitic bivalve shells grown under highly controlled temperatures (1-18°C), which we combine with clumped isotope data from natural and synthetic aragonites from a wide range of temperatures (1-850°C). We observe no discernible offset in clumped isotope values between aragonitic foraminifera, mollusks, and abiogenic aragonites or between aragonites and calcites, eliminating the need for a mineral-specific calibration or acid fractionation factor. However, due to non-linear behavior of the clumped isotope thermometer, including high-temperature (>100°C) datapoints in linear clumped isotope calibrations causes them to underestimate temperatures of cold (1-18°C) carbonates by 2.7±2.0°C (95% confidence level). Therefore, clumped isotope-based paleoclimate reconstructions should be calibrated using samples with well constrained formation temperatures close to those of the samples.

Experimental burial diagenesis of aragonitic biocarbonates: from organic matter loss to abiogenic calcite formation

Abstract. Carbonate biological hard tissues are valuable archives of environmental information. However, this information can be blurred or even completely lost as hard tissues undergo diagenetic alteration. This is more likely to occur in aragonitic skeletons because bioaragonite often transforms into calcite during diagenesis. For reliably using aragonitic skeletons as geochemical proxies, it is necessary to understand in depth the diagenetic alteration processes that they undergo. Several works have recently investigated the hydrothermal alteration of aragonitic hard tissues during short-term experiments at high temperatures (T > 160 ∘C). In this study, we conduct long-term (4 and 6 months) hydrothermal alteration experiments at 80 ∘C using burial-like fluids. We document and evaluate the changes undergone by the outer and inner layers of the shell of the bivalve Arctica islandica, the prismatic and nacreous layers of the hard tissue of the gastropod Haliotis ovina, and the skeleton of the coral Porites sp. combining a variety of analytical tools (X-ray diffraction, thermogravimetry analysis, laser confocal microscopy, scanning electron microscopy, electron backscatter diffraction and atomic force microscopy). We demonstrate that this approach is the most adequate to trace subtle, diagenetic-alteration-related changes in aragonitic biocarbonate structural hard materials. Furthermore, we unveil that the diagenetic alteration of aragonitic biological hard tissues is a complex multi-step process where major changes occur even at the low temperature used in this study, well before any aragonite into calcite transformation takes place. Alteration starts with biopolymer decomposition and concomitant generation of secondary porosity. These processes are followed by abiogenic aragonite precipitation that partially or totally obliterates the secondary porosity. Only subsequently does the transformation of the aragonite into calcite occur. The kinetics of the alteration process is highly dependent on primary microstructural features of the aragonitic biomineral. While the skeleton of Porites sp. remains virtually unaltered for the entire duration of the conducted experiments, Haliotis ovina nacre undergoes extensive abiogenic aragonite precipitation. The outer and inner shell layers of Arctica islandica are significantly affected by aragonite transformation into calcite. This transformation is extensive for the prismatic shell layer of Haliotis ovina. Our results suggest that the majority of aragonitic fossil archives are overprinted, even those free of clear diagenetic alteration signs. This finding may have major implications for the use of these archives as geochemical proxies.

Crystallographic and chemical signatures in coral skeletal aragonite

Corals nucleate and grow aragonite crystals, organizing them into intricate skeletal structures that ultimately build the world’s coral reefs. Crystallography and chemistry have profound influence on the material properties of these skeletal building blocks, yet gaps remain in our knowledge about coral aragonite on the atomic scale. Across a broad diversity of shallow-water and deep-sea scleractinian corals from vastly different environments, coral aragonites are remarkably similar to one another, confirming that corals exert control on the carbonate chemistry of the calcifying space relative to the surrounding seawater. Nuances in coral aragonite structures relate most closely to trace element chemistry and aragonite saturation state, suggesting the primary controls on aragonite structure are ionic strength and trace element chemistry, with growth rate playing a secondary role. We also show how coral aragonites are crystallographically indistinguishable from synthetic abiogenic aragonite analogs precipitated from seawater under conditions mimicking coral calcifying fluid. In contrast, coral aragonites are distinct from geologically formed aragonites, a synthetic aragonite precipitated from a freshwater solution, and mollusk aragonites. Crystallographic signatures have future applications in understanding the material properties of coral aragonite and predicting the persistence of coral reefs in a rapidly changing ocean.

On the coordination of Mg2+ in aragonite: Ab-initio absorption spectroscopy and isotope fractionation study

Magnesium in biogenic aragonite skeletons is widely used to infer the geochemical conditions under which the minerals precipitated. However, because molecular speciation of Mg2+ in the aragonite crystal structure remains uncertain, questions are often posed about the reliability and utility of Mg as a paleoenvironment proxy. In this study, we investigated the Mg2+ coordination in abiogenic aragonite by applying first-principles density functional theory (DFT). We report for the first time a Mg2+-site disordered structure model of aragonite: substituted Mg2+ is five-fold coordinated and induces substantial disorder in the bond distances that depends on the relative positions of Mg2+ sites. Using the site disorder model, DFT qualitatively reproduces the key features of experimental Mg K-edge X-ray absorption near-edge structure (XANES) spectra of aragonite. DFT also resolves a long-standing conflict between experimental and theoretical studies pertaining to the enrichment of 26Mg in aragonite relative to calcite. The Boltzmann-averaged 26Mg/24Mg reduced partition function ratios were calculated in the order of aqueous Mg2+ > Mg-doped aragonite > Mg-doped calcite. The disorder structure model is likely applicable to the substitution of cations with radii smaller than the radius of Ca2+ ions in aragonite. Our study provides atomistic insight into metal substitution effects on the metal content and isotope fractionation in biogenic aragonite, which are critical for developing a reliable paleoenvironment proxy.

Sub-annual fluorescence measurements of coral skeleton: relationship between skeletal luminescence and terrestrial humic-like substances

Some massive coral core slices reveal luminescent bands under ultraviolet light, which have been attributed to terrestrial humic acids in the skeleton. Coral luminescence has therefore been used to reconstruct past climate and hydrological variability. However, it has remained unresolved how closely coral luminescence at sub-annual resolution is related to terrestrial humic acid concentrations. This study presents a solution-based fluorescence method to quantify terrestrial humic substances in less than 4 mg of coral powder. The results show that in corals from Malaysia and Singapore, the luminescence green-to-blue ratio is correlated with skeletal concentrations of terrestrial humic substances (R2 > 0.40, p < 0.001) at two sites that are exposed to terrestrial dissolved organic matter from peatlands on Sumatra. In contrast, coral cores from two other sites located far from major terrestrial organic matter sources show lower green-to-blue values and no convincing correlation with fluorescence intensity of terrestrial humic substances in the skeleton. Abiogenic aragonite precipitation experiments with both terrestrial and marine organic matter sources confirmed that terrestrial humic substances are readily incorporated into aragonite, but not fluorescent organic matter from marine sources. The results of this study suggest that in coral cores with high luminescence green-to-blue ratios (> 0.6) and large downcore variability (range of ≥ 0.05), the green-to-blue ratio is strongly linked to variation in terrestrial humic substances. Coral cores therefore have the potential to reconstruct past variation in terrigenous dissolved organic carbon fluxes.

Kinetic and Metabolic Isotope Effects in Zooxanthellate and Non-zooxanthellate Mediterranean Corals Along a Wide Latitudinal Gradient

Many calcifying organisms exert significant biological control over the construction and composition of biominerals which are thus generally depleted in oxygen-18 and carbon-13 relative to the isotopic ratios of abiogenic aragonite. The skeletal δ18O and δ13C values of specimens of Mediterranean zooxanthellate (Balanophyllia europaea and Cladocora caespitosa) and non-zooxanthellate corals (Leptopsammia pruvoti and Caryophyllia inornata) were assessed along an 8° latitudinal gradient along Western Italian coasts, spanning ~2 °C and ~37 W m-2 of annual average sea surface temperature and solar radiation (surface values), respectively. Seawater δ18O and δ13CDIC were surprisingly constant along the ~850 km latitudinal gradient while a ~2 and ~4 ‰ variation in skeletal δ18O and a ~4 and ~9 ‰ variation in skeletal δ13C was found in the zooxanthellate and non-zooxanthellate species, respectively. Albeit Mediterranean corals considered in this study are slow growing, only a limited number of non-zooxanthellate specimens exhibited skeletal δ18O equilibrium values while all δ13C values in the four species were depleted in comparison to the estimated isotopic equilibrium with ambient seawater, suggesting that these temperate corals cannot be used for thermometry-based seawater reconstruction. Calcification rate, linear extension rate and skeletal density were unrelated to isotopic compositions. The fact that skeletal δ18O and δ13C of zooxanthellate corals were confined to a narrower range at the most isotopically depleted end compared to non-zooxanthellate corals, suggests that the photosynthetic activity may restrict corals to a limited range of isotopic composition, away from isotopic equilibrium for both isotopes. Our data show that individual corals within the same species express the full range of isotope fractionation. These results suggest that metabolic and/or kinetic effects may act as controlling factors of isotope variability of skeleton composition along the transect, and that precipitation of coral skeletal aragonite occurs under controlling kinetic biological processes, rather than thermodynamic control, by yet unidentified mechanisms.

The Origin and Role of Organic Matrix in Coral Calcification: Insights From Comparing Coral Skeleton and Abiogenic Aragonite

Understanding the mechanisms of coral calcification is critical for accurately projecting coral reef futures under ocean acidification and warming. Recent suggestions that calcification is primarily controlled by organic molecules and the biological activity of the coral polyp imply that ocean acidification may not affect skeletal accretion. The basis for these suggestions relies heavily on correlating the presence of organic matter with the orientation and disorder of aragonite crystals in the skeleton, carrying the assumptions that organic matter observed in the skeleton was produced by the polyp to control calcification. Here we use Raman spectroscopy to test whether there are differences in organic matter content between coral skeleton and abiogenic aragonites precipitated from seawater, both before and after thermal annealing (heating). We measured the background fluorescence and intensity of C-H bonding signals in the Raman spectra, which are commonly attributed to coral polyp-derived skeletal organic matrix (SOM) and have been used to map its distribution. Surprisingly, we found no differences in either fluorescence or C-H bonding between abiogenic aragonite and coral skeleton. Annealing reduced the molecular disorder in coral skeleton, potentially due to removal of organic matter, but the same effect was also observed in the abiogenic aragonites. The presence of organic molecules in the abiogenic aragonites is further supported by measurements of N content and δ15N. Together, our data suggest that some of what has been interpreted in previous studies as polyp-derived SOM may actually be seawater-sourced organic matter or some other signal not unique to biogenic aragonite. Finally, we create a high-resolution Raman map of a Pocillopora skeleton to demonstrate how patterns of fluorescence and elevated calcifying fluid aragonite saturation state along centers of calcification are consistent with both biological and physico-chemical controls. Our aim is to advance discussion on biological mediation of calcification and the implications for coral resilience in a high-CO2 world.

Reviews and syntheses: Revisiting the boron systematics of aragonite and their application to coral calcification

Abstract. The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B∕Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B∕Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.

Coral calcifying fluid aragonite saturation states derived from Raman spectroscopy

Abstract. Quantifying the saturation state of aragonite (ΩAr) within the calcifying fluid of corals is critical for understanding their biomineralization process and sensitivity to environmental changes including ocean acidification. Recent advances in microscopy, microprobes, and isotope geochemistry enable the determination of calcifying fluid pH and [CO32−], but direct quantification of ΩAr (where ΩAr = [CO32−][Ca2+]∕Ksp) has proved elusive. Here we test a new technique for deriving ΩAr based on Raman spectroscopy. First, we analysed abiogenic aragonite crystals precipitated under a range of ΩAr from 10 to 34, and we found a strong dependence of Raman peak width on ΩAr with no significant effects of other factors including pH, Mg∕Ca partitioning, and temperature. Validation of our Raman technique for corals is difficult because there are presently no direct measurements of calcifying fluid ΩAr available for comparison. However, Raman analysis of the international coral standard JCp-1 produced ΩAr of 12.3 ± 0.3, which we demonstrate is consistent with published skeletal Mg∕Ca, Sr∕Ca, B∕Ca, δ11B, and δ44Ca data. Raman measurements are rapid ( ≤ 1 s), high-resolution ( ≤ 1 µm), precise (derived ΩAr ± 1 to 2 per spectrum depending on instrument configuration), accurate ( ±2 if ΩAr &lt; 20), and require minimal sample preparation, making the technique well suited for testing the sensitivity of coral calcifying fluid ΩAr to ocean acidification and warming using samples from natural and laboratory settings. To demonstrate this, we also show a high-resolution time series of ΩAr over multiple years of growth in a Porites skeleton from the Great Barrier Reef, and we evaluate the response of ΩAr in juvenile Acropora cultured under elevated CO2 and temperature.

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates – Relation between textural control on effective element fluxes and resulting carbonate phase

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9M MgCl2 and 0.015M SrCl2 at 200°C. The replacement of aragonite by a Ca-bearing magnesite and a Mg–Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure.

Effects of organic solvents on stable isotopic composition of otolith and abiogenic aragonite

Otoliths are important proxies for climate change and ecological studies and are typically stored in glycerin or ethanol for preservation. This study is the first attempt to assess the isotopic effects of these preservatives on carbon and oxygen isotope ratios of otolith aragonite. Experimental tests from the 4th annulus of dried Pacific halibut otoliths were compared to samples from the same otoliths collected after 30day storage in either glycerin or ethanol. In addition, isotopic measurements of abiogenic pure aragonite samples soaked in glycerin, ethanol, acetone, dichlorom (DCM), and methanol were compared to the initial values following the same protocol. No δ18O effect was observed for otoliths stored in glycerin or ethanol; and no isotopic effects (both δ18O and δ13C) were observed for abiogenic pure aragonite stored in the five organic solvents commonly used in geochemical laboratories. Although there was a significant but very small difference in carbon isotope ratios of halibut otoliths, the shift was of a barely measureable magnitude and the statistically significant difference only in δ13C values may result from the inhomogeneous composition and structure of otoliths. Thus we concluded that there was no isotopic exchange during organic solvent storage or preservative interference in the isotope ratio measurements.

The influence of temperature and vital effects on magnesium isotope variability in Porites and Astrangia corals

The magnesium isotope composition (δ26Mg) of sub-annually and bulk-sampled Porites corals is presented and suggests that the coral–seawater fractionation factor (∆26Mg) is temperature-dependent with a sensitivity of ~0.03‰°C−1. Although the apparent temperature dependence of ∆26Mg in Porites corals could be used empirically to reconstruct paleoclimate, its temperature sensitivity is about three times that of abiogenic aragonites, which indicates that kinetic and/or biologically-induced processes (collectively known as vital effects) are also important. Comparison with data from abiogenic aragonite precipitation experiments suggests that ∆26Mg vital effects vary seasonally in Porites. The ∆26Mg of skeleton deposited in winter is within the analytical error of abiogenic aragonite, but that of skeletal aragonite grown during summer exhibits significantly smaller fractionations that may be associated with light-enhanced calcification. The observed vital effect is consistent with <0.03% of coral Mg occurring as fluid inclusions, possibly associated with amorphous calcium carbonate (ACC). Other mechanisms such as surface entrapment and/or pH-induced changes in Mg speciation may also affect ∆26Mg, but cannot be evaluated with current data. However, the observed vital effect is not consistent with the isotope fractionation expected from Rayleigh processes, ion attachment/detachment kinetics or diffusion. Furthermore, the ∆26Mg of symbiotic and asymbiotic Astrangia corals is within analytical error, and indicates that vital effects cannot be attributed to the presence of photosymbionts. Some data suggest that the offset between coral and abiogenic aragonite ∆26Mg may be proportional to that for oxygen isotope fractionations, raising the possibility that vital effects in both isotope systems may be influenced by a common mechanism. Although the presence of vital effects and analytical limitations will complicate the development of a ∆26Mg-based paleothermometer, it may still be a valuable tool for reconstructing seawater δ26Mg or investigating biomineralization processes, especially when applied as part of a multi-proxy approach.

Rayleigh-based, multi-element coral thermometry: A biomineralization approach to developing climate proxies

This study presents a new approach to coral thermometry that deconvolves the influence of water temperature on skeleton composition from that of “vital effects”, and has the potential to provide estimates of growth temperatures that are accurate to within a few tenths of a degree Celsius from both tropical and cold-water corals. Our results provide support for a physico-chemical model of coral biomineralization, and imply that Mg 2+ substitutes directly for Ca 2+ in biogenic aragonite. Recent studies have identified Rayleigh fractionation as an important influence on the elemental composition of coral skeletons. Daily, seasonal and interannual variations in the amount of aragonite precipitated by corals from each “batch” of calcifying fluid can explain why the temperature dependencies of elemental ratios in coral skeleton differ from those of abiogenic aragonites, and are highly variable among individual corals. On the basis of this new insight into the origin of “vital effects” in coral skeleton, we developed a Rayleigh-based, multi-element approach to coral thermometry. Temperature is resolved from the Rayleigh fractionation signal by combining information from multiple element ratios (e.g., Mg/Ca, Sr/Ca, Ba/Ca) to produce a mathematically over-constrained system of Rayleigh equations. Unlike conventional coral thermometers, this approach does not rely on an initial calibration of coral skeletal composition to an instrumental temperature record. Rather, considering coral skeletogenesis as a biologically mediated, physico-chemical process provides a means to extract temperature information from the skeleton composition using the Rayleigh equation and a set of experimentally determined partition coefficients. Because this approach is based on a quantitative understanding of the mechanism that produces the “vital effect” it should be possible to apply it both across scleractinian species and to corals growing in vastly different environments. Where instrumental temperature records are available, a Rayleigh-based framework allows the effects of stress on coral calcification to be identified on the basis of anomalies in the skeletal composition.

Sr/Ca and Mg/Ca ratios of ontogenetically old, long-lived bivalve shells ( Arctica islandica) and their function as paleotemperature proxies

The Sr/Ca and Mg/Ca ratios of many biogenic skeletons provide useful paleotemperature estimates. As yet however, it has remained largely impossible to obtain such information from bivalve shells. In the present study, metal-to-calcium values in the hinge plate (aragonite, outer shell layer) of four ontogenetically old (85 to 374 year-old) specimens of the long-lived bivalve, Arctica islandica, were measured on a LA–ICP–MS. The shells were collected alive in 1868, 1986 and 2003 from three different localities around Iceland. With increasing ontogenetic age and decreasing growth rate, a distinct trend toward increasing Sr/Ca (max. 5.17 mmol/mol) and Mg/Ca values (max. 0.89 mmol/mol) and greater variance were observed. Three potential explanations for these trends include a reduced capacity for element selection due to cell ageing, changing metabolism and/or a relative increase in the number of organic-rich (= Mg-rich) and organic-poor (= Sr-rich) shell portions through ontogeny. Partition coefficients however, remained far below 1, indicating that physiology exerted a strong control over the element partitioning between the shells and the ambient water. After mathematical elimination of these vital effects, residuals exhibited a highly significant negative correlation (e.g., age-detrended Sr/Ca data: R = − 0.64, R 2 = 0.41, p < 0.0001, growth rate-detrended Mg/Ca data: R = − 0.52, R 2 = 0.27, p < 0.0001) with sea surface temperature. These results are in good agreement with results obtained from the precipitation of abiogenic aragonite. The results of the present study can help to develop new techniques to extract environmental signals from the metal-to-calcium ratios of bivalve shells.

Compositional and morphological features of aragonite precipitated experimentally from seawater and biogenically by corals

The morphology and composition of abiogenic (synthetic) aragonites precipitated experimentally from seawater and the aragonite accreted by scleractinian corals were characterized at the micron and nano scale. The synthetic aragonites precipitated from supersaturated seawater solutions as spherulites, typically 20–100 μm in diameter, with aggregates of sub-micron granular materials occupying their centers and elongate (fibrous) needles radiating out to the edge. Using Sr isotope spikes, the formation of the central granular material was shown to be associated with high fluid pH and saturation state whereas needle growth occurred at lower pH and saturation state. The granular aggregates have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers. Two types of crystals are identified in the coral skeleton: aggregates of sub-micron granular material and bundles of elongate (fibrous) crystals that radiate out from the aggregates. The granular materials are found in “centers of calcification” and in fine bands that transect the fiber bundles. They have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers. The observed relationship between seawater saturation state and crystal morphology and composition in the synthetic aragonites was used as a framework to interpret observations of the coral skeleton. We propose that coral skeletal growth can be viewed as a cyclical process driven by changes in the saturation state of the coral’s calcifying fluids. When saturation state is high, granular crystals precipitate at the tips of the existing skeletal elements forming the centers of calcification. As the saturation state decreases, aragonitic fibres grow in bundles that radiate out from the centers of calcification.

Provenance of microcrystalline carbonate cement in limestone–marl alternations (LMA): aragonite mud or molluscs?

Aragonite derived from marine molluscs is evaluated as the source for microcrystalline carbonate cements of limestone–marl alternations (LMA). Calculations demonstrate that extremely low levels of mollusc-derived aragonite, well below the production rates of molluscs in modern marine settings, could have provided sufficient carbonate to cement examples of Ordovician, Silurian and Jurassic LMA in non-tropical or tropical settings. It is likely that even in the Palaeozoic molluscs provided sufficient carbonate entirely to source microcrystalline cements of LMA. Autochthonous molluscan aragonite is the only viable aragonite precursor for LMA microcrystalline cements of cool-water settings where temperatures precluded calcified algae and abiotic carbonate precipitation. In ‘calcite seas’ where Mg:Ca ratios inhibited both abiogenic aragonite precipitation and aragonite generation by calcified algae, molluscan aragonite was again the most likely main contributor. In some epeiric seas where brackish wedges switched off the shallow-water carbonate mud factories molluscan aragonite is the parsimonious source of carbonate for LMA microcrystalline cements.

Compositional variability in a cold‐water scleractinian, Lophelia pertusa: New insights into “vital effects”

We analyzed Sr/Ca and Mg/Ca ratios in the thecal wall of Lophelia pertusa, a cold‐water coral, using SIMS ion microprobe techniques. The wall grows by simultaneous upward extension and outward thickening. Compositional variability displays similar trends along the upward and outward growth axes. Sr/Ca and Mg/Ca ratios oscillate systematically and inversely. The sensitivity of Lophelia Sr/Ca ratios to the annual temperature cycle (−0.18 mmol · mol−1/°C) is twice as strong as that exhibited by tropical reef corals, and four times as strong as the temperature dependence of Sr/Ca ratios of abiogenic aragonites precipitated experimentally from seawater. A comparison of the skeletal composition of Lophelia with results from precipitation calculations carried out using experimentally determined partition coefficients suggests that both temperature‐dependent element partitioning and seasonal changes in the mass fraction of aragonite precipitated from the calcifying fluid influence the composition of Lophelia skeleton. Results from calculations that combine these effects reproduce both the exaggerated amplitude of the Sr/Ca and Mg/Ca oscillations and the inverse relationship between Sr/Ca and Mg/Ca ratios.

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg 2+, Ca 2+, Sr 2+, and Ba 2+ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO 3 IV. The coprecipitation of Sr 2+ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta 33, 1–17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr 2+, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral. 80, 1179–1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta 60, 5013–5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta 68, 1473–1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.

Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

The uptake of Cd 2+ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO 3 solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO 3 solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.